CN101838290A - Functionalized ionic liquid containing a phosphorus and oxygen structure, and preparation method and application thereof - Google Patents
Functionalized ionic liquid containing a phosphorus and oxygen structure, and preparation method and application thereof Download PDFInfo
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- CN101838290A CN101838290A CN201010108113A CN201010108113A CN101838290A CN 101838290 A CN101838290 A CN 101838290A CN 201010108113 A CN201010108113 A CN 201010108113A CN 201010108113 A CN201010108113 A CN 201010108113A CN 101838290 A CN101838290 A CN 101838290A
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Abstract
The invention relates to functionalized ionic liquid containing a phosphorus and oxygen structure with a general formula of A+ B-, which is characterized in that A+ is shown in a formula (I), and R 1 and R 2 are defined in the specification; and B- is Cl-, Br-, I -, BF4-, PF6-, NO3-, CF3SO3-, [(CF3SO2) 2N] - or CH3CO2-. The invention also relates to a method for preparing ionic liquid with the formula of A + B-, which comprises the following steps: a compound in a formula (III) is reacted with a compound in a formula (II ') to obtain a compound in a formula (II'') , and then a compound in a formula (II'') is reacted with a compound in a formula (IV) to obtain a halide ionic liquid A + B-, wherein B- is Cl-, Br-or I-, and ionic liquids with the other anions can be obtained by carrying out the ion exchange of the halide ionic liquid. The invention also relates to application of the ionic liquids in extraction of uranium from uranium-containing water systems. HO-(CH2) nCH2-X (III).
Description
Technical field
The present invention relates to a kind of imidazole type ion liquid, relate in particular to a kind of functionalized ion liquid (TSILs, Task Specific Ionic Liquids or FILs, FunctionalizedIonic Liquids) of phosphorous oxide structure.The invention still further relates to aforementioned preparation method of ionic liquid and this ion liquid application, the especially application of uranium in extraction uranium-bearing water system.
Background technology
Ionic liquid is compared with ionogen with traditional organic solvent, has a series of outstanding advantages: (1) does not almost have vapour pressure, non-volatile, colourless, tasteless; (2) bigger equilibrium temperature scope is arranged, the electrochemical stability potential window of better chemical stability and broad; (3) can regulate its solvability by the design of zwitterion to inorganics, organism and polymkeric substance.Owing to have the performance of above excellence, therefore be regarded as " green " solvent, can substitute the conventional volatile organic compound that brings pollution to atmosphere, be used for organic synthesis and liquid-liquid extraction system ([1] Li Hongyu, Liu Zhengping. uranium ore smelting .2008,27,86-91), greatly avoided the wasting of resources and problem of environmental pollution because of using in a large number and volatilizing and cause.
In the process to extraction separation uranium such as uranium-bearing water system such as uranium ore leach liquor, uranium-containing waste water, spent fuel and high activity liquid wastes, extraction is one of main means.With the alkyl imidazole hydrophobic type ionic liquid at room temperature of routine as [C
8Mim] [PF
6] or [C
4Mim] [PF
6] be thinner, with the uranium extraction agent tributyl phosphate composite uranium that is used for extracting the uranium-bearing water system such as (TBP), can obtain higher extraction efficiency ([2] P.Giridhar, K.A.Venkatesan, T.G.Srinivasan.P.R.Vasudeva Rao, Journal of Radioanalytical and Nuclear Chemistry, 2005,265,31-38), but exist extraction system to produce triphasic problem, thereby hinder carrying out smoothly of extraction process.This be because: the extracted species of tributyl phosphate and uranyl ion generation is at ionic liquid [C
8Mim] [PF
6] and [C
4Mim] [PF
6] in solubleness less, in extraction process, reached saturated, thereby from organic phase, separated out and become third phase.Yet functionalized ion liquid of the present invention is not found triphasic generation when extraction contains uranium solution, thereby helps carrying out smoothly of extraction process.
The present invention utilizes the notion of functionalized ion liquid, traditional extraction agent functional group is incorporated in the ionic liquid cationic structural, design synthesizes the functionalized ion liquid of a class novelty, make ionic liquid be thinner be again extraction agent, reduce the complexity of component in the extraction phase, helped the optimization of extraction process.
Summary of the invention
The object of the present invention is to provide the task-specific ionic liquid of the phosphorous oxide structure of a class.
Another object of the present invention is to provide above-mentioned preparation method of ionic liquid.
A further object of the present invention is to provide the application of above-mentioned ionic liquid uranium in extraction uranium-bearing water system.
According to a first aspect of the invention, providing a kind of general formula is A
+B
-The ionic liquid of phosphorous oxide structure, wherein said A
+Shown in (I):
Wherein each variable-definition is as follows:
R
1For having the straight or branched alkyl of 1-8 carbon atom, be preferably straight or branched alkyl with 1-4 carbon atom; With
R
2Phosphate-based for shown in the formula (II):
Wherein
R
3And R
4For having the straight or branched alkyl of 1-8 carbon atom, be preferably straight or branched alkyl independently of one another with 1-5 carbon atom;
N is 0-8, is preferably the integer of 0-3; With
* represent R
2Tie point with nitrogen heteroatom in the formula (I);
And
Described B
-Be Cl
-, Br
-, I
-, BF
4 -, PF
6 -, NO
3 -, CF
3SO
3 -, [(CF
3SO
2)
2N]
-Or CH
3CO
2 -
In ionic liquid of the present invention, R
1For having the straight or branched alkyl of 1-8 carbon atom.As R
1Example, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl, Sec-Hexyl, n-heptyl and n-octyl.Preferably, R
1For having the straight or branched alkyl of 1-4 carbon atom, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl to this.
In ionic liquid of the present invention, R
3And R
4For having the straight or branched alkyl of 1-8 carbon atom, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl, Sec-Hexyl, n-heptyl and n-octyl independently of one another to this.Preferably, R
3And R
4For having the straight or branched alkyl of 1-5 carbon atom, for example be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl or sec.-amyl sec-pentyl secondary amyl independently of one another independently of one another.
In ionic liquid of the present invention, n is the integer of 0-8, that is, n is 0,1,2,3,4,5,6,7 or 8; Preferably, n is the integer of 0-3, that is, n is 0,1,2 or 3.
In particularly preferred embodiments, ionic liquid of the present invention is:
1-(di(2-ethylhexyl)phosphate normal-butyl ethyl ester)-3-Methylimidazole bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole hexafluorophosphate,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bis trifluoromethyl sulfimide salt,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-methyl imidazolium tetrafluoroborate,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-N-Methylimidazoleacetic salt,
1-(tricresyl phosphate n-butyl)-3-Methylimidazole bromide,
1-(tricresyl phosphate n-butyl)-3-Methylimidazole hexafluorophosphate,
1-(tricresyl phosphate n-butyl)-3-Methylimidazole bis trifluoromethyl sulfimide salt,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazolium bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazoles hexafluorophosphate,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazoles bis trifluoromethyl sulfimide salt,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazolium bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazoles hexafluorophosphate, or
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazoles bis trifluoromethyl sulfimide salt.
According to a further aspect in the invention, provide preparation the present invention ion liquid method.
The ion liquid preparation of the present invention is according to the negatively charged ion B in the ionic liquid
-Difference, and adopt different preparation methods.Preparation B
-Be halide anion X
-(comprise Cl
-, Br
-And I
-) ionic liquid, adopt quaterisation; Preparation B
-Be non-halide anion Y
-(comprise BF
4 -, PF
6 -, NO
3 -, CF
3SO
3 -, [(CF
3SO
2)
2N]
-And CH
3CO
2 -) ionic liquid, adopt replacement(metathesis)reaction.
Therefore, the invention provides a kind of preparation wherein B of the present invention
-Be the ion liquid method of the phosphorous oxide structure of halide anion, this method comprises:
(1) make the halohydrin of following formula (III):
HO-(CH
2)
nCH
2-X (III)
Wherein n in the general formula (II) definition and X be Cl, Br or I substituting group, react with the alkyl phosphite of following formula (II '):
R in its Chinese style (II ')
3And R
4Separately suc as formula defining in (II), obtain the phosphoric acid ester of formula (II "):
N, R in its Chinese style (II ")
3And R
4Separately suc as formula defining in (II) and X is Cl, Br or I substituting group; And
(2) phosphoric acid ester of the formula that step (1) obtains (II ") and the substituted imidazole compounds of following formula (IV) are reacted,
R wherein
1Define suc as formula (I) is middle,
Obtain general formula A of the present invention
+B
-The ionic liquid of phosphorous oxide structure, B wherein
-Be Cl
-, Br
-Or I
-Negatively charged ion, and A
+General formula A as mentioned
+B
-The middle definition.
The reaction of top step (1) is typical phase-transfer-catalyzed reactions, and this reaction is conventional to those skilled in the art.
Method produced according to the present invention advantageously in the superincumbent step (1), before formula (III) compound and formula (II ') compound is reacted, need be carried out purification process with them separately.Formula (II ') compound can be with equimolar amount or molar excess use with respect to formula (III) compound, and for example the mol ratio of the former with the latter is 1.3: 1～1: 1, and more preferably the former uses with molar excess with respect to the latter.
The reaction of formula (III) compound and formula (II ') compound is carried out in the presence of solvent usually.This solvent is included in any solvent that does not participate in this chemical reaction under the reaction conditions of formula (III) compound and formula (II ') compound and be liquid form, can mention tetracol phenixin, methylene dichloride, 1 to this, 2-ethylene dichloride, 1,1,1-trichloroethane, toluene, acetone, N, dinethylformamide, tetrahydrofuran (THF) etc. preferably use the solvent of the double solvents of tetracol phenixin and methylene dichloride formation as this reaction.The consumption of solvent is conventional, as long as formula (III) compound and formula (II ') compound is successfully reacted; Usually, the consumption of solvent (the especially double solvents of tetracol phenixin and methylene dichloride formation) should make: the ratio of the cumulative volume cumulative volume of mixed solvent and reactant (that is, formula (III) compound and formula (II ') compound) is 3: 1～5: 1.For the purpose of the present invention, when the double solvents that tetracol phenixin and methylene dichloride are constituted during as the reaction solvent in the step (1), the volume ratio of tetracol phenixin and methylene dichloride is generally 2: 1～and 3: 1, for example 2.2: 1.
In the above-mentioned preparation method's of the present invention step (1), interpolation or hybrid mode for solvent and reactant, can be in advance formula (III) compound and formula (II ') compound be dissolved in respectively and forms solution in the solvent, and then with these two kinds of solution mixing, a kind of being dissolved in formula (III) compound and formula (the II ') compound can also be formed solution in the solvent, then the another kind in this solution and formula (III) compound and formula (the II ') compound is mixed, for example formula (III) compound dissolution is formed solution in solvent, then formula (II ') compound slowly is added drop-wise in the solution of formula (III) compound for preparing.
In above-mentioned preparation method of the present invention, phase-transfer-catalyzed reactions in the step (1) can also two kinds not mutual solvents carry out in the presence of mutually, the existence of phase-transfer catalyst makes the alkyl phosphite of the halohydrin of formula (III) and formula (II ') to react in the two-phase mixed solvent.This mixed solvent can and be selected from tetracol phenixin, methylene dichloride, 1 for aqueous sodium hydroxide solution or potassium hydroxide aqueous solution, 2-ethylene dichloride, 1,1,1-trichloroethane, toluene, acetone, N, any or multiple mixture in this group solvent of dinethylformamide and tetrahydrofuran (THF).Preferred this mixed solvent is the mixture of aqueous sodium hydroxide solution or potassium hydroxide aqueous solution and tetracol phenixin and methylene dichloride.When using this class mixed solvent, aqueous sodium hydroxide solution or potassium hydroxide aqueous solution use with the concentration of 25～50wt% usually.The consumption of mixed solvent is conventional, and usually, the cumulative volume of mixed solvent is 3: 1～5: 1 with the ratio of reactant cumulative volume.
In above-mentioned preparation method of the present invention, the phase-transfer-catalyzed reactions in the step (1) carries out in the presence of catalyzer, and this selection of catalysts and consumption are conventional.Usually, the catalyzer that is used for the inventive method catalyzed reaction comprises tetrabutylammonium chloride and Tetrabutyl amonium bromide.
The temperature of reaction and the reaction pressure of the reaction in the above-mentioned preparation method's of the present invention the step (1) are conventional.Usually, this reaction can be carried out under 0～15 ℃, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually, preferred 3～5 hours.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.
Phase-transfer-catalyzed reactions among the above-mentioned preparation method of the present invention can also carry out under inert atmosphere, and the selection of this rare gas element is conventional.Usually, the rare gas element that can be used for the inventive method comprises nitrogen and argon gas, preferred high pure nitrogen and/or high-purity argon gas.
After the reaction of step (1) was finished, separated product from reaction mixture obtained the phosphoric acid ester of formula (II ").This lock out operation is conventional to those skilled in the art.For example with methylene dichloride reaction mixture is diluted earlier, after the filtering separation, use 2wt% dilute hydrochloric acid, deionized water wash organic phase successively, use anhydrous sodium sulfate drying again, revolve at last to steam and remove most of organic solvent.In addition, advantageously with products therefrom vacuum-drying, removing volatile component remaining in the product, thus the phosphoric acid ester of the formula of obtaining (II ").
After the phosphoric acid ester of the formula of making (II "), make itself and formula (IV) compound generation quaternary ammonium reaction, thereby obtain wherein B of the present invention
-Be Cl
-, Br
-Or I
-Anion ion liquid.This reaction is conventional to those skilled in the art.
Method produced according to the present invention advantageously in step (2), before quaternary ammonium reaction takes place, must be carried out purification process with formula (IV) compound.The phosphoric acid ester of formula (II ") can be used with equimolar amount or molar excess with respect to formula (IV) compound, and for example the mol ratio of the former with the latter is 1.25: 1～1: 1, and more preferably the former uses with molar excess with respect to the latter.
The reaction of the phosphate compound of formula (IV) compound and formula (II ") is carried out in the presence of solvent-free usually.
In the above-mentioned preparation method's of the present invention step (2), interpolation or hybrid mode for two kinds of reactants, both can be with the phosphoric acid ester of formula (IV) compound and formula (II ") with itself disposable having joined in the reaction vessel, also can in advance formula (IV) compound slowly be added drop-wise in the phosphoric acid ester of formula (II ") or the phosphate compound of formula (II ") is added in formula (IV) compound.
The temperature of reaction and the reaction pressure of the reaction in the above-mentioned preparation method's of the present invention the step (2) are conventional.Usually, this reaction can be carried out under 20～120 ℃, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～48 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.In addition advantageously, this reaction is under refluxad carried out.
After the reaction of step (2) was finished, separated product from reaction mixture obtained wherein B
-Be Cl
-, Br
-Or I
-Anionic ionic liquid of the present invention.For example, behind the separatory, product 50 ℃ of following vacuum-dryings, with volatile component remaining in the deionizing liquid, thereby is obtained wherein B with ethyl acetate washing reaction mixture repeatedly
-Be Cl
-, Br
-Or I
-Anionic ionic liquid of the present invention.
As the ion liquid negatively charged ion B of the present invention
-During for non-halide-ions, the ion liquid method of preparation the present invention comprises:
(a) according to above-mentioned preparation wherein B of the present invention
-Ion liquid method for halide anion makes B
-Halide ions liquid for halide anion; And
(b) make the halide ions liquid that obtains in the step (a) and the salt of following formula V carry out replacement(metathesis)reaction or ion exchange reaction:
M
+Y
- (V)
M wherein
+Be H
+, Li
+, Na
+, K
+, Rb
+, Cs
+, Ag
+, Pb
+Or NH
4 +Positively charged ion, and Y
-Be BF
4 -, PF
6 -, NO
3 -, CF
3SO
3 -, [(CF
3SO
2)
2N]
-Or CH
3CO
2 -, obtain general formula A of the present invention
+B
-The ionic liquid of phosphorous oxide structure, B wherein
-Be BF
4 -, PF
6 -, NO
3 -, CF
3SO
3 -, [(CF
3SO
2)
2N]
-Or CH
3CO
2 -, and A
+As hereinbefore defined.
Therefore, as the ion liquid negatively charged ion B of the present invention
-During for non-halide anion, the ion liquid method of preparation the present invention comprises:
(a) according to above-mentioned preparation wherein B of the present invention
-Ion liquid method for halide anion makes B
-Halide ions liquid for halide anion; And
(b1) make halide ions liquid and the silver nitrate aqueous solution reaction that obtains in the step (a), make the halogen ion generate precipitation, thereby obtain wherein B
-Ionic liquid of the present invention for nitrate radical; Perhaps
(b2) the halide ions liquid that obtains in the step (a) and Tetrafluoroboric acid or its an alkali metal salt are reacted in the presence of dehydrated alcohol, obtain wherein B
-Ionic liquid of the present invention for tetrafluoroborate; Perhaps
(b3) make the halide ions liquid that obtains in the step (a) and the reactant aqueous solution of phosphofluoric acid or its an alkali metal salt, obtain wherein B
-Ionic liquid of the present invention for hexafluoro-phosphate radical; Perhaps
(b4) make the reactant aqueous solution of lithium, sodium or the sylvite of the halide ions liquid that obtains in the step (a) and bis trifluoromethyl sulfimide, separatory obtains wherein B
-Ionic liquid of the present invention for bis trifluoromethyl sulfimide root; Perhaps
(b5) make the halide ions liquid that obtains in the step (a) and the reactant aqueous solution of lead acetate or silver acetate, make the halogen ion generate precipitation, thereby obtain wherein B
-Ionic liquid of the present invention for acetate moiety; Perhaps
(b6) make the halide ions liquid that obtains in the step (a) and the reactant aqueous solution of trifluoromethanesulfonic acid, make the halogen ion generate haloid acid, thereby obtain wherein B
-Ionic liquid of the present invention for the trifluoromethanesulfonic acid root.
In above-mentioned preparation method's step (b1), advantageously, with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of Silver Nitrate.With respect to halide ions liquid, Silver Nitrate preferably uses with equimolar amount.The temperature of the reaction in the step (b1) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction in the step (b1) makes the halogen ion (comprise Cl
-, Br
-And I
-Negatively charged ion) form with silver halide precipitates.After reaction is finished, filter, and, preferably revolve steaming, promptly obtain B the filtrate evaporation
-Ionic liquid of the present invention for nitrate radical.
In an especially preferred embodiment, in step (b1), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with the Silver Nitrate of the equimolar amount that is aqueous solution form more afterwards, at room temperature reaction, make halide anion generate silver halide precipitation, filter afterwards, and with the filtrate evaporation, thereby wherein B obtained
-Ionic liquid of the present invention for nitrate radical.
In above-mentioned preparation method's step (b2), advantageously, with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the dehydrated alcohol, mix with Tetrafluoroboric acid or its an alkali metal salt more afterwards.With respect to Tetrafluoroboric acid or its an alkali metal salt, this halide ions liquid can use or excessive use with equimolar amount, and preferably the two uses with equimolar amount.The temperature of the reaction in the step (b2) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction is isolated lower floor's oil phase after finishing, and uses the deionized water repetitive scrubbing, and the halogen negatively charged ion (comprises Cl in washings
-, Br
-And I
-Negatively charged ion) (this can check by Silver Nitrate and verify,, silver nitrate aqueous solution is splashed into whether observation has precipitation to judge in the washings that is) promptly obtains wherein B till
-Ionic liquid of the present invention for tetrafluoroborate.
For the present invention, an alkali metal salt of above-mentioned Tetrafluoroboric acid refers to the lithium of Tetrafluoroboric acid, sodium, potassium, rubidium and cesium salt, preferably its lithium, sodium and sylvite.
In an especially preferred embodiment, in step (b2), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the dehydrated alcohol, mix with Tetrafluoroboric acid or its an alkali metal salt of equimolar amount more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid of the present invention for tetrafluoroborate.
In above-mentioned preparation method's step (b3), advantageously, with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of phosphofluoric acid or its an alkali metal salt.With respect to phosphofluoric acid or its an alkali metal salt, this halide ions liquid can use or excessive use with equimolar amount, and preferably the two uses with equimolar amount.The temperature of the reaction in the step (b3) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction is isolated lower floor's oil phase after finishing, and uses the deionized water repetitive scrubbing, and the halogen negatively charged ion (comprises Cl in washings
-, Br
-And I
-Negatively charged ion) (this can check by Silver Nitrate and verify,, silver nitrate aqueous solution is splashed into whether observation has precipitation to judge in the washings that is) promptly obtains wherein B till
-Ionic liquid of the present invention for hexafluoro-phosphate radical.
For the present invention, an alkali metal salt of above-mentioned phosphofluoric acid refers to the lithium of phosphofluoric acid, sodium, potassium, rubidium and cesium salt, preferably its lithium, sodium and sylvite.
In an especially preferred embodiment, in step (b3), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with phosphofluoric acid or its an alkali metal salt of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid of the present invention for hexafluoro-phosphate radical.
In above-mentioned preparation method's step (b4), advantageously, with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of lithium, sodium or the sylvite of bis trifluoromethyl sulfimide.With respect to lithium, sodium or the sylvite of bis trifluoromethyl sulfimide, this halide ions liquid can use or excessive use with equimolar amount, and preferably the two uses with equimolar amount.The temperature of the reaction in the step (b4) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and any agitator that is suitable for this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction is isolated lower floor's oil phase after finishing, and uses the deionized water repetitive scrubbing, and the halogen negatively charged ion (comprises Cl in washings
-, Br
-And I
-Negatively charged ion) (this can check by Silver Nitrate and verify,, silver nitrate aqueous solution is splashed into whether observation has precipitation to judge in the washings that is) promptly obtains wherein B till
-Ionic liquid of the present invention for bis trifluoromethyl sulfimide root.
In an especially preferred embodiment, in step (b4), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with lithium, sodium or the sylvite of the bis trifluoromethyl sulfimide of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid of the present invention for bis trifluoromethyl sulfimide root.
In above-mentioned preparation method's step (b5), advantageously, with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of lead acetate or silver acetate.With respect to lead acetate or silver acetate, this halide ions liquid preferably uses with stoichiometric quantity.Temperature of reaction in the step (b5) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and is applicable to that any agitator of this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction in the step (b5) makes the halogen ion (comprise Cl
-, Br
-And I
-Negatively charged ion) form with lead halide or silver halide precipitates.After reaction is finished, filter,, promptly obtain B the filtrate evaporation
-Ionic liquid of the present invention for acetate moiety.
In an especially preferred embodiment, in step (b5), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with the lead acetate or the silver acetate of the stoichiometric quantity that is aqueous solution form more afterwards, at room temperature reaction, make halide anion generate lead halide or silver halide precipitation, filter afterwards,, thereby obtain wherein B the filtrate evaporation
-Ionic liquid of the present invention for acetate moiety.
In above-mentioned preparation method's step (b6), advantageously, with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, afterwards again with the aqueous solution of trifluoromethanesulfonic acid.With respect to trifluoromethanesulfonic acid, halide ions liquid preferably uses with equimolar amount.Temperature of reaction in the step (b6) has no particular limits, and advantageously at room temperature carries out, and reaction pressure is preferably autogenous pressure.The time of this reaction is depended on multiple factor, for example productive rate and temperature of reaction, and for economic aim, this reaction was carried out 1～24 hour usually.This reaction can also under agitation be carried out, and is applicable to that any agitator of this purpose can use, and comprises paddle stirrer, magnetic stirring apparatus etc.Reaction is isolated lower floor's oil phase after finishing, and uses the deionized water repetitive scrubbing, and the halogen negatively charged ion (comprises Cl in washings
-, Br
-And I
-Negatively charged ion) (this can check by Silver Nitrate and verify,, silver nitrate aqueous solution is splashed into whether observation has precipitation to judge in the washings that is) promptly obtains B till
-Ionic liquid of the present invention for the trifluoromethanesulfonic acid root.
In an especially preferred embodiment, in step (b6), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with the trifluoromethanesulfonic acid of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid of the present invention for the trifluoromethanesulfonic acid root.Ionic liquid of the present invention can be used for the extraction of metallic element, especially can be used for extracting the uranium of uranium-bearing water system.
Therefore, the present invention also provides ionic liquid of the present invention in extraction uranium-bearing water system, the especially application of uranium in uranium-bearing water systems such as extraction uranium ore leach liquor, uranium-containing waste water, spent fuel and high activity liquid waste.
The present invention compared with prior art has following unusual effect:
1, the present invention is to provide the task-specific ionic liquid of a class novelty, developed ion liquid new variety;
2, ionic liquid provided by the invention is owing to have the phosphorus oxide structure, can be used as the extraction agent and the thinner of uranium and other radionuclide in the uranium-bearing water system;
3, the present invention can prepare a series of ionic liquids with different carbon chain lengths and phosphorus oxide structure;
4, quaternized, replacement(metathesis)reaction is adopted in ion liquid preparation provided by the invention, and equipment used is few, and step is simple; The reaction conditions gentleness, cost is lower, and environmental pollution is few, is suitable for industrial production;
5, in the ionic liquid required for protection in the present invention; have several uranium element to be had excellent extracting power, as 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bis trifluoromethyl sulfimide salt, 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole hexafluorophosphate etc.At ambient temperature, 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bis trifluoromethyl sulfimide salt can extract uranium, its partition ratio D＞10, percentage extraction E＞90% in nitric acid system.This shows that ionic liquid of the present invention can be used for the extraction of uranium element in the uranium-bearing water system.
Embodiment
Following examples are used to illustrate ionic liquid of the present invention and preparation method thereof, but these embodiment do not constitute limitation of the scope of the invention.
The preparation of embodiment 1:1-(di(2-ethylhexyl)phosphate normal-butyl ethyl ester)-3-Methylimidazole bromide
To being housed, agitator, constant pressure funnel, temperature take into account in the 250mL four-hole boiling flask of airway, the NaOH aqueous solution (30mL), the ethylene bromohyrin (12.5g that add 25wt%, 0.1mol), tetracol phenixin (25mL), methylene dichloride (25mL) and Tetrabutyl amonium bromide (0.36g, 1.12mmol), stirring makes its mixing, and ice-water bath control mixed system temperature is at 10～15 ℃; (24.3g 0.125mol) with after tetracol phenixin (30mL) mixes in constant pressure funnel, dropwise splashes in the above-mentioned ethylene bromohyrin mixed system, dropwises, and removes ice-water bath, and system at room temperature continued to react 3 hours with phosphorous acid di-n-butyl ester.Having reacted the back dilutes system with methylene dichloride (20mL), filter, after the filtrate that obtains is washed three times with 2wt% dilute hydrochloric acid (20mL) washing three times, deionized water (20mL), use anhydrous sodium sulfate drying again, revolve steam remove tetracol phenixin and methylene dichloride after, obtain phosphoric acid 2-bromoethyl di-n-butyl ester.
With phosphoric acid 2-bromoethyl di-n-butyl ester (3.17g, 0.01mol) with the N-Methylimidazole (0.82g 0.01mol) mixes, room temperature reaction 48 hours, product washs purifying with ethyl acetate, vacuum-drying 24 hours obtains the water white transparency thick liquid.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 75%.(FITR(cm
-1)：3142，3061，2963，2876，1736，1572，1467，1381，1295，1170，1026，906，862，787，665。
1H?NMR(D
2O)：δ＝8.50(s，1H)，7.32(m，2H)，4.01-4.15(m，2H)，3.70-3.93(m，6H)，3.62(s，3H)，1.59-1.69(m，4H)，1.32-1.41(m，4H)，0.85-0.93(t，6H)ppm。Heat decomposition temperature: 110 ℃.
The preparation of embodiment 2:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide
To being housed, agitator, constant pressure funnel, temperature take into account in the 250mL four-hole boiling flask of airway, the NaOH aqueous solution (30mL), the 3-bromopropyl alcohol (13.9g that add 25wt%, 0.1mol), tetracol phenixin (25mL), methylene dichloride (25mL) and Tetrabutyl amonium bromide (0.36g, 1.12mmol), stirring makes its mixing, and ice-water bath control mixed system temperature is at 10～15 ℃; (24.3g 0.125mol) with after tetracol phenixin (30mL) mixes in constant pressure funnel, dropwise splashes in the mixed system of above-mentioned 3-bromopropyl alcohol, dropwises, and removes ice-water bath, and system at room temperature continued to react 3 hours with phosphorous acid di-n-butyl ester.Having reacted the back dilutes system with methylene dichloride (20mL), filter, after the filtrate that obtains uses 2wt% dilute hydrochloric acid (20mL) washing three times, deionized water (20mL) to wash three times successively, use anhydrous sodium sulfate drying again, revolve steam remove tetracol phenixin and methylene dichloride after, obtain phosphoric acid 3-bromo propyl group di-n-butyl ester.
With phosphoric acid 3-bromo propyl group di-n-butyl ester (3.31g, 0.01mol) with the N-Methylimidazole (0.82g 0.01mol) mixes, room temperature reaction 48 hours, product washs purifying with ethyl acetate, vacuum-drying 24 hours obtains the water white transparency thick liquid.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 80%.(FITR(cm
-1)：3142，3061，2960，2873，1736，1572，1465，1373，1267，1170，1028，906，862，756，621。
1H?NMR(D
2O)：δ＝8.63(s，1H)，7.38(s，1H)，7.33(s，1H)，4.21-4.24(t，2H)，3.96-3.98(m，6H)，3.75(s，3H)，2.13-2.16(m，2H)，1.51-1.54(m，4H)，1.24-1.25(m，4H)，0.75-0.79(t，6H)ppm。Heat decomposition temperature: 100 ℃.
The preparation of embodiment 3:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole hexafluorophosphate
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide 4.13g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 1.84g Potassium Hexafluorophosphate (0.01mol) and be dissolved in the 20mL deionized water, with these two kinds of solution mixing of gained, stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying obtained light yellow thick liquid after 24 hours with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 73%.FTIR(cm
-1)：3168，2963，2875，1577，1466，1391，1263，1171，1029，840，740，623，557。
1HNMR(CDCl
3)：δ＝8.57(s，1H)，7.28(s，1H)，7.22(s，1H)，4.24-4.27(t，2H)，3.95-4.00(m，6H)，3.83(s，3H)，2.10-2.20(m，2H)，1.56-1.63(m，4H)，1.29-1.38(m，4H)，0.85-0.88(t，6H)ppm。Heat decomposition temperature: 260 ℃.
The preparation of embodiment 4:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bis trifluoromethyl sulfimide salt
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide 4.13g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 2.87g (0.01mol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying 24 hours obtains colourless transparent liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 70%.FTIR(cm
-1)：3157，3119，2965，2877，1576，1467，1431，1353，1264，1196，1138，1058，1031，803，789，761，740，653，617，570。
1H?NMR(CDCl
3)，δ＝8.85(s，1H)，7.44(s，1H)，7.21(s，1H)，4.29-4.32(m，2H)，3.96-4.01(m，6H)，3.88(s，3H)，2.18-2.19(m，2H)，1.58-1.61(m，4H)，1.31-1.36(m，4H)，0.87-0.89(t，6H)ppm。Heat decomposition temperature: 230 ℃.
The preparation of embodiment 5:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-methyl imidazolium tetrafluoroborate
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide 4.13g (0.01mol), be dissolved in the 30mL dehydrated alcohol, take by weighing sodium tetrafluoroborate 1.09g (0.01mol), join in the aforementioned solution, stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying 24 hours obtains colourless viscous liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 50%.FTIR(cm
-1)：3159，3119，2964，2877，1576，1471，1396，1370，1338，1259，1171，1027，877，763，623。
1H?NMR(D
2O)：δ＝8.59(s，1H)，7.34(d，2H)，4.17-4.21(m，4H)，3.97-4.01(m，4H)，3.69-3.72(s，3H)，3.42-3.46(m，2H)，2.10-2.14(m，4H)，1.74-1.80(m，4H)，0.76(m，6H)ppm。Heat decomposition temperature: 110 ℃.
The preparation of embodiment 6:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-N-Methylimidazoleacetic salt
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide 4.13g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 1.62g (5mmol) lead acetate and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Remove by filter insolubles, filtrate is revolved steaming to remove big water gaging, vacuum-drying was removed residuary water and volatile constituent in 24 hours, obtained light yellow transparent liquid.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 55%.(FITR(cm
-1)：3093，2962，2875，1709，1573，1471，1396，1332，1266，1171，1024，927，878，695。
1H?NMR(D
2O)：δ＝8.61(s，1H)，7.35(s，1H)，7.30(s，1H)，4.18-4.21(t，2H)，3.97-4.02(m，3H)，3.69-3.74(m，6H)，2.09-2.15(m，2H)，1.74-1.79(m，11H)，0.75-0.76(t，6H)ppm。Heat decomposition temperature: 100 ℃.
The preparation of embodiment 7:1-(tricresyl phosphate n-butyl)-3-Methylimidazole bromide
To being housed, agitator, constant pressure funnel, temperature take into account in the 250mL four-hole boiling flask of airway, the NaOH aqueous solution (30mL), the 4-bromobutanol (15.3g that add 25wt%, 0.1mol), tetracol phenixin (25mL), methylene dichloride (25mL) and Tetrabutyl amonium bromide (0.36g, 1.12mmol), stirring makes its mixing, and ice-water bath control mixed system temperature is at 10～15 ℃; (24.3g 0.125mol) with after tetracol phenixin (30mL) mixes in constant pressure funnel, dropwise splashes in the mixed system of above-mentioned 4-bromobutanol, dropwises, and removes ice-water bath, and system at room temperature continued to react 3 hours with phosphorous acid di-n-butyl ester.Having reacted the back dilutes system with methylene dichloride (20mL), filter, after the filtrate that obtains is washed three times with 2wt% dilute hydrochloric acid (20mL) washing three times, deionized water (20mL), use anhydrous sodium sulfate drying again, revolve steam remove tetracol phenixin and methylene dichloride after, obtain phosphatase 24-bromo butyl di-n-butyl ester.
With phosphatase 24-bromo butyl di-n-butyl ester (3.45g, 0.01mol) with the N-Methylimidazole (0.82g 0.01mol) mixes, room temperature reaction 48 hours, product washs purifying with ethyl acetate, vacuum-drying 24 hours obtains the water white transparency thick liquid.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 74%.(FITR(cm
-1)：3140，3059，2960，2873，1734，1570，1465，1370，1267，1170，1030，904，862，756，621。
1H?NMR(D
2O)：δ＝8.78(s，1H)，7.37(s，1H)，7.34(s，1H)，4.70(s，2H)，4.01-4.07(m，6H)，3.70(s，3H)，1.65-1.70(m，6H)，1.30-1.41(m，6H)，0.71-0.80(t，6H)。Heat decomposition temperature: 110 ℃.
The preparation of embodiment 8:1-(tricresyl phosphate n-butyl)-3-Methylimidazole hexafluorophosphate
Take by weighing 1-(tricresyl phosphate n-butyl)-3-Methylimidazole bromide 4.27g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 1.84g Potassium Hexafluorophosphate (0.01mol) and be dissolved in the 20mL deionized water, with these two kinds of solution mixing of gained, stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying obtained light yellow thick liquid after 24 hours with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 75%.FTIR(cm
-1)：3164，2963，2873，1570，1461，1390，1263，1171，1029，840，745，623，556。
1H?NMR(CDCl
3)：δ＝8.90(s，1H)，7.30(s，1H)，7.25(s，1H)，4.70(t，2H)，4.03-4.06(m，6H)，3.90(s，3H)，1.67-1.71(m，6H)，1.31-1.41(m，6H)，0.88-0.91(t，6H)ppm。Heat decomposition temperature: 250 ℃.
The preparation of embodiment 9:1-(tricresyl phosphate n-butyl)-3-Methylimidazole bis trifluoromethyl sulfimide salt
Take by weighing 1-(tricresyl phosphate n-butyl)-3-Methylimidazole bromide 4.27g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 2.87g (0.01mol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying 24 hours obtains colourless transparent liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 74%.FTIR(cm
-1)：3162，3120，2965，2875，1576，1467，1431，1353，1265，1194，1138，1058，1031，803，789，759，653，620，570。
1H?NMR(CDCl
3)，δ＝8.86(s，1H)，7.45(s，1H)，7.24(s，1H)，4.69(t，2H)，4.04-4.07(m，6H)，3.89(s，3H)，1.58-1.61(m，6H)，1.31-1.38(m，6H)，0.89-0.92(t，6H)ppm。Heat decomposition temperature: 230 ℃.
The preparation of embodiment 10:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazolium bromide
Repeat the preparation method of embodiment 2, make N-normal-butyl imidazoles, obtain yellow thick liquid but general's N-Methylimidazole wherein changes.Products therefrom is confirmed as the compound described in the title through infrared spectra and nmr analysis, and productive rate is 60%.FTIR(cm
-1)：3056，2960，2874，1564，1468，1395，1369，1273，1168，1024，877，754，664。
1H?NMR(D
2O)：δ＝8.72(s，1H)，7.41(d，2H)，4.22-4.25(t，2H)，3.94-4.08(m，8H)，1.61-1.83(m，8H)，1.10-1.20(m，6H)，0.75-0.79(m，9H)ppm。Heat decomposition temperature: 100 ℃.
The preparation of embodiment 11:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazoles hexafluorophosphate
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazolium bromide 4.55g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 1.84g Potassium Hexafluorophosphate (0.01mol) and be dissolved in the 20mL deionized water, with these two kinds of solution mixing of gained, stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying obtained yellow thick liquid after 24 hours with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 55%.FTIR(cm
-1)：3161，3116，2964，2877，1567，1470，1397，1370，1262，1166，1024，845，754，740，555。
1H?NMR(CDCl
3)：δ＝8.77(s，1H)，7.50(s，1H)，7.28(s，1H)，4.35-4.38(t，2H)，4.15-4.18(m，2H)，4.04-4.08(m，4H)，3.80-3.83(m，4H)，2.23-2.29(m，2H)，1.91-2.01(m，2H)，1.83-1.89(m，4H)，1.30-1.43(m，4H)，0.94-0.98(t，9H)ppm。Heat decomposition temperature: 180 ℃.
The preparation of embodiment 12:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazoles bis trifluoromethyl sulfimide salt
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazolium bromide 4.55g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 2.87g (0.01mol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying 24 hours obtains yellow thick liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 75%.FTIR(cm
-1)：3148，3115，2966，2878，1566，1513，1470，1397，1352，1197，1138，1058，916，880，788，761，740，656，616，570。
1H?NMR(CDCl
3)，δ＝8.98(s，1H)，7.28-7.54(d，2H)，4.37-4.41(t，2H)，4.05-4.20(m，6H)，3.80-3.84(m，4H)，2.24-2.30(m，2H)，1.96-1.99(m，2H)，1.79-1.94(m，4H)，1.33-1.42(m，4H)，0.94-0.96(t，9H)ppm。Heat decomposition temperature: 200 ℃.
The preparation of embodiment 13:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazolium bromide
Repeat the preparation method of embodiment 2, make N-isobutyl-imidazoles, obtain the water white transparency thick liquid but general's N-Methylimidazole wherein changes.Products therefrom is confirmed as the compound described in the title through infrared spectra and nmr analysis, and productive rate is 55%.FTIR(cm
-1)：3132，3058，2962，2874，1563，1470，1393，1370，1266，1167，1021，878，759，637。
1HNMR(D
2O)：δ＝8.73(s，1H)，7.40-7.42(d，2H)，4.23-4.26(t，2H)，3.72-3.74(m，8H)，1.92-2.02(m，7H)，1.79-1.84(m，4H)，0.77-0.79(d，12H)ppm。Heat decomposition temperature: 100 ℃.
The preparation of embodiment 14:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazoles hexafluorophosphate
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazolium bromide 4.55g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 1.84g Potassium Hexafluorophosphate (0.01mol) and be dissolved in the 20mL deionized water, with these two kinds of solution mixing of gained, stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying obtained the water white transparency thick liquid after 24 hours with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 60%.FTIR(cm
-1)：3160，3116，2965，2878，1566，1471，1396，1371，1262，1166，1024，845，756，740，640，555。
1H?NMR(CDCl
3)：δ＝8.74(s，1H)，7.51(s，1H)，7.29(s，1H)，4.36-4.39(m，4H)，3.97-4.08(m，6H)，3.80-3.83(m，2H)，2.24-2.30(m，4H)，2.10-2.18(m，1H)，1.90-1.99(m，4H)，0.94-0.96(d，12H)ppm。Heat decomposition temperature: 200 ℃.
The preparation of embodiment 15:1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazoles bis trifluoromethyl sulfimide salt
Take by weighing 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazolium bromide 4.55g (0.01mol), be dissolved in the 30mL deionized water, take by weighing 2.87g (0.01mol) bis trifluoromethyl sulfimide lithium and be dissolved in the 20mL deionized water.These two kinds of solution of gained are mixed, and stirring reaction is 24 hours under room temperature.Outwell the upper strata water, till the bromine ion-containing (Silver Nitrate check) not, vacuum-drying 24 hours obtains colourless transparent liquid with deionized water repetitive scrubbing lower floor oil phase.Products therefrom is confirmed to be the compound described in the title through infrared spectra and nmr analysis, and productive rate is 62%.FTIR(cm
-1)：3148，3114，2967，2879，1565，1472，1396，1352，1195，1137，1058，1028，880，820，788，761，740，656，619，570。
1H?NMR(CDCl
3)，δ＝8.98(s，1H)，7.56(s，1H)，7.28(s，1H)，4.39-4.42(m，4H)，3.99-4.09(m，6H)，3.80-3.83(m，2H)，2.24-2.30(m，4H)，2.09-2.18(m，1H)，1.92-1.99(m，4H)，0.94-0.97(m，12H)ppm。Heat decomposition temperature: 200 ℃.
Embodiment 16:
In separating funnel, adding 1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bis trifluoromethyl sulfimide salt that 5mL makes by embodiment 4 and the uranium concentration of 5mL successively is the aqueous nitric acid of 60mg/L.This separating funnel is put into 25 ℃ of water bath with thermostatic control vibrators, and mechanical oscillation left standstill analysis after 30 minutes.Analyze and find partition ratio D＞10 of uranium, percentage extraction E＞90%.
Claims (11)
1. general formula is A
+B
-The ionic liquid of phosphorous oxide structure, wherein said A
+Shown in (I):
Wherein each variable-definition is as follows:
R
1For having the straight or branched alkyl of 1-8 carbon atom, be preferably straight or branched alkyl with 1-4 carbon atom; With
R
2Phosphate-based for shown in the formula (II):
Wherein
R
3And R
4For having the straight or branched alkyl of 1-8 carbon atom, be preferably straight or branched alkyl independently of one another with 1-5 carbon atom;
N is 0-8, is preferably the integer of 0-3; With
* represent R
2Tie point with nitrogen heteroatom in the formula (I);
And
Described B
-Be Cl
-, Br
-, I
-, BF
4 -, PF
6 -, NO
3 -, CF
3SO
3 -, [(CF
3SO
2)
2N]
-Or CH
3CO
2 -
2. the ionic liquid shown in claim 1, it is:
1-(di(2-ethylhexyl)phosphate normal-butyl ethyl ester)-3-Methylimidazole bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole hexafluorophosphate,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-Methylimidazole bis trifluoromethyl sulfimide salt,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-methyl imidazolium tetrafluoroborate,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-N-Methylimidazoleacetic salt,
1-(tricresyl phosphate n-butyl)-3-Methylimidazole bromide,
1-(tricresyl phosphate n-butyl)-3-Methylimidazole hexafluorophosphate,
1-(tricresyl phosphate n-butyl)-3-Methylimidazole bis trifluoromethyl sulfimide salt,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazolium bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazoles hexafluorophosphate,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-normal-butyl imidazoles bis trifluoromethyl sulfimide salt,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazolium bromide,
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazoles hexafluorophosphate, or
1-(di(2-ethylhexyl)phosphate normal-butyl n-propyl ester)-3-isobutyl-imidazoles bis trifluoromethyl sulfimide salt.
3. one kind prepares as the desired wherein B of claim 1
-Ion liquid method for halide anion comprises:
(1) make the halohydrin of following formula (III):
HO-(CH
2)
nCH
2-X (III)
Wherein in the general formula (II) of n in the claim 1 definition and X be Cl, Br or I substituting group, react with the alkyl phosphite of following formula (II '),
R in its Chinese style (II ')
3And R
4Each defines in the formula (II) in the claim 1 freely, obtains the phosphoric acid ester of formula (II "):
N, R in its Chinese style (II ")
3And R
4Each defines in the formula (II) in the claim 1 freely and X is Cl, Br or I substituting group; And
(2) phosphoric acid ester of the formula that step (1) obtains (II ") and the substituted imidazole compounds of following formula (IV) are reacted,
R wherein
1Such as in the formula in the claim 1 (I) definition,
Obtain general formula A
+B
-The ionic liquid of phosphorous oxide structure, B wherein
-Be Cl
-, Br
-Or I
-Negatively charged ion, and A
+As claim 1 formula of A
+B
-The middle definition.
4. as the desired method of claim 3, it is characterized in that, and formula (II ') with equimolar amount or molar excess use, the mol ratio of preferred the former with the latter is 1.3: 1～1: 1 to compound with respect to formula (III) compound.
5. as claim 3 or 4 desired methods, it is characterized in that, one or more solvents that are selected from down group that are reflected at of formula (III) compound and formula (II ') compound carry out under existing: tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,1,1-trichloroethane, toluene, acetone, N, dinethylformamide and tetrahydrofuran (THF) group are preferably used the solvent of the double solvents of tetracol phenixin and methylene dichloride formation as this reaction.
6. as claim 3 or 4 desired methods, it is characterized in that, being reflected at aqueous sodium hydroxide solution or potassium hydroxide aqueous solution and being selected from tetracol phenixin, methylene dichloride, 1 in the step (1), 2-ethylene dichloride, 1,1,1-trichloroethane, toluene, acetone, N, carry out under any or multiple mixture of this group of dinethylformamide and tetrahydrofuran (THF) in solvent exists as solvent, preferably at the mixture of aqueous sodium hydroxide solution or potassium hydroxide aqueous solution and tetracol phenixin and methylene dichloride as carrying out in the presence of the solvent.
7. as each desired method among the claim 3-6, it is characterized in that the catalyzer that the reaction in the step (1) is used is tetrabutylammonium chloride and/or Tetrabutyl amonium bromide.
8. one kind prepares as desired wherein B in the claim 1
-Be BF
4 -, PF
6 -, NO
3 -, CF
3SO
3 -, [(CF
3SO
2)
2N]
-Or CH
3CO
2 -Ionic liquid A
+B
-Method, comprising:
(a) prepare as the desired wherein B of claim 1 according to each method in the claim 3～7
-Be Cl
-, Br
-Or I
-Anionic halide ions liquid A
+B
-, A wherein
+As claim 1 mutual-through type A
+B
-Define; And
(b1) make halide ions liquid and the silver nitrate aqueous solution reaction that obtains in the step (a), make the halogen ion generate precipitation, thereby obtain ionic liquid A
+B
-, B wherein
-Be nitrate radical, and A
+As claim 1 mutual-through type A
+B
-Define; Perhaps
(b2) the halide ions liquid that obtains in the step (a) and Tetrafluoroboric acid or its an alkali metal salt are reacted in the presence of dehydrated alcohol, obtain ionic liquid A
+B
-, B wherein
-Be tetrafluoroborate, and A
+As claim 1 mutual-through type A
+B
-Define; Perhaps
(b3) make the halide ions liquid that obtains in the step (a) and the reactant aqueous solution of phosphofluoric acid or its an alkali metal salt, obtain ionic liquid A
+B
-, B wherein
-Be hexafluoro-phosphate radical, and A
+As claim 1 mutual-through type A
+B
-Define; Perhaps
(b4) make the reactant aqueous solution of lithium, sodium or the sylvite of the halide ions liquid that obtains in the step (a) and bis trifluoromethyl sulfimide, separatory obtains ionic liquid A
+B
-, B wherein
-Be bis trifluoromethyl sulfimide root, and A
+As claim 1 mutual-through type A
+B
-Define; Perhaps
(b5) make the halide ions liquid that obtains in the step (a) and the reactant aqueous solution of lead acetate or silver acetate, make the halogen ion generate precipitation, thereby obtain ionic liquid A
+B
-, B wherein
-Be acetate moiety, and A
+As claim 1 mutual-through type A
+B
-Define; Perhaps
(b6) make the halide ions liquid that obtains in the step (a) and the reactant aqueous solution of trifluoromethanesulfonic acid, make the halogen ion generate haloid acid, thereby obtain ionic liquid A
+B
-, B wherein
-Be the trifluoromethanesulfonic acid root, and A
+As claim 1 mutual-through type A
+B
-Define.
9. method as claimed in claim 8 is characterized in that,
In step (b1), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with the Silver Nitrate of the equimolar amount that is aqueous solution form more afterwards, at room temperature reaction, make halide anion generate silver halide precipitation, filter afterwards, and with the filtrate evaporation, thereby wherein B obtained
-Ionic liquid A for nitrate radical
+B
-Perhaps
In step (b2), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the dehydrated alcohol, mix with Tetrafluoroboric acid or its an alkali metal salt of equimolar amount more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid A for tetrafluoroborate
+B
-Perhaps
In step (b3), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with phosphofluoric acid or its an alkali metal salt of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid A for hexafluoro-phosphate radical
+B
-Perhaps
In step (b4), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with lithium, sodium or the sylvite of the bis trifluoromethyl sulfimide of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid A for bis trifluoromethyl sulfimide root
+B
-Perhaps
In step (b5), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with the lead acetate or the silver acetate of the stoichiometric quantity that is aqueous solution form more afterwards, at room temperature reaction, make halide anion generate lead halide or silver halide precipitation, filter afterwards,, thereby obtain wherein B the filtrate evaporation
-Ionic liquid A for acetate moiety
+B
-Perhaps
In step (b6), with the B that obtains in the step (a)
-For the halide ions liquid of halide anion is dissolved in the deionized water, mix with the trifluoromethanesulfonic acid of the equimolar amount that is aqueous solution form more afterwards, at room temperature stirring reaction is 1～24 hour, isolate lower floor's oil phase, use the deionized water repetitive scrubbing, in washings till the halogen negatively charged ion, thereby obtain wherein B
-Ionic liquid A for the trifluoromethanesulfonic acid root
+B
-
10. method as claimed in claim 8 or 9 is characterized in that Tetrafluoroboric acid an alkali metal salt and phosphofluoric acid an alkali metal salt are respectively Tetrafluoroboric acid and phosphofluoric acid lithium, sodium, potassium, rubidium or cesium salt separately.
11. extracting the uranium-bearing water system as claim 1 or 2 desired ionic liquids, the especially application of uranium in extraction uranium ore leach liquor, uranium-containing waste water, spent fuel and high activity liquid waste.
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